1,2,4- thiadiazole compounds and use thereof

ABSTRACT

1,2,4-Thiadiazole compounds represented by the formula (1) have excellent control activities against harmful arthropods:  
                 
 
wherein R 1  represents C3-C7 alkynyl group optionally substituted one or more halogen atom(s); R 2  a represents a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxy group, a C1-C4 alkylthio group, a cyano group, or a nitro group, and n is an integer of 0 to 5, provided that, when n is an integer of 2 or more, respective R 2 s may be the same or different; A represents an oxygen atom, a sulfur atom, a single bond, a CR 3 R 4  group, or NR 5 ; R 3  and R 4  represent each independently a hydrogen atom or a C1-4 alkyl group; and R 5  represent a hydrogen and the like.

TECHNICAL FIELD

The present invention relates to a 1,2,4-thiadiazole compound and usethereof.

BACKGROUND ART

It is known that a certain 1,3,4-thiadiazole compound can be used as anactive ingredient of an agent for controlling harmful arthropods(DE3030661, etc.).

However, harmful arthropod controlling activity of this1,3,4-thiadiazole compound is not sufficient, and a compound having moreexcellent harmful arthropod controlling activity is sought.

DISCLOSURE OF THE INVENTION

The present inventor has studied intensively in order to find out acompound having excellent pesticidal activity, and have found excellentharmful arthropod controlling activity in a 1,2,4-thiadiazole compound.Thus, the present invention has been completed.

That is, the present invention provides a 1,2,4-thiadiazole compoundrepresented by the formula (1):

wherein R¹ represents a C3-C7 alkynyl group optionally substituted withone or more halogen atom(s), R² represents a halogen atom, a C1-C4 alkylgroup, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxygroup, a C1-C4 alkylthio group, a cyano group or a nitro group, nrepresents an integer of 0 to 5, provided that, when n represents aninteger of 2 or more, respective R²s may be the same or different,

A represents an oxygen atom, a sulfur atom, a single bond, a CR³R⁴ groupor a NR⁵ group, R³ and R⁴ represent each independently a hydrogen atomor a C1-C4 alkyl group, and R⁵ represents a hydrogen atom, a C1-C7 alkylgroup, a haloalkyl group, a C2-C4(alkoxyalkyl) group, aC2-C4(haloalkoxyalkyl) group, a C3-C6 alkenyl group, a C3-C6 haloalkenylgroup, a C3-C7 alkynyl group, a C3-C7 haloalkynyl group or a cyanomethylgroup (herein after referred to as the compound of the presentinvention); and an arthropod controlling composition containing the sameas an active ingredient.

In the compound of the present invention, examples of the C3-C7 alkynylgroup optionally substituted with one or more halogen atom(s)represented by R¹ include a 2-propynyl group, a 2-butynyl group, a4-fluoro-2-butynyl group, a 1-methyl-2-butynyl group, a 2-pentynylgroup, a 4,4-dimethyl-2-pentynyl group, a 3-chloro-2-propynyl group, a3-bromo-2-propynyl group, a 3-iodo-2-propynyl group, a1-methyl-2-propynyl group, a 3-butynyl group, and a 3-pentynyl group.

Examples of the halogen atom represented by R² include a fluorine atom,a chlorine atom, and a bromine atom, examples of the C1-C4 alkyl grouprepresented by R² include a methyl group, an ethyl group, and a1,1-dimethylethyl group, examples of the C1-C4 haloalkyl grouprepresented by R² include a trifluoromethyl group, a difluoromethylgroup, and a pentafluoroethyl group, examples of the C1-C4 alkoxy grouprepresented by R² include a methoxy group and an ethoxy group, examplesof the C1-C4 haloalkoxy group represented by R² include atrifluoromethoxy group and a pentafluoroethoxy group, examples of theC1-C4 alkylthio group represented by R² include a methylthio group, andan ethylthio group.

Examples of the CR³R⁴ group represented by A include a CH₂ group, aCH(CH₃) group, and examples of the NR⁵ group represented by A include aNH group, a NCH₃ group, a NC₂H₅ group, a NCH₂OCH₃ group, a NCH₂OC₂H₅group and a NCH₂CN group.

Examples of the compound of the present invention include a1,2,4-thiadiazole compound represented by the formula (1) wherein R¹ isa 2-propynyl group; a 1,2,4-thiadiazole compound represented by theformula (1) wherein R¹ is a 2-butynyl group; a 1,2,4-thiadiazolecompound represented by the formula (1) wherein R¹ is a 2-pentynylgroup; a 1,2,4-thiadiazole compound represented by the formula (1)wherein A is a single bond; a 1,2,4-thiadiazole compound represented bythe formula (1) wherein R¹ is a 2-propynyl group, and A is a singlebond; a 1,2,4-thiadiazole compound represented by the formula (1)wherein R¹ is a 2-butynyl group, and A is a single bond; a1,2,4-thiadiazole compound represented by the formula (1) wherein R¹ isa 2-pentynyl group, and A is a single bond; a 1,2,4-thiadiazole compoundrepresented by the formula (1) wherein n is 0; a 1,2,4-thiadiazolecompound represented by the formula (1) wherein n is 1 or 2, and R² is ahalogen atom.

Then, a process for preparing the compound of the present invention willbe explained. The compound of the present invention can be prepared, forexample, by reacting a compound represented by the formula (2) and R¹OHin the presence of a base.

wherein A, R¹, R² and n are as defined above, and m represents 1 or 2.

The reaction is usually performed in a solvent. Examples of the solventto be used include ethers such as tetrahydrofuran, acid amides such asN,N-dimethylformamide, dimethyl sulfoxide, and a mixture thereof.Examples of the base used in the reaction include inorganic bases suchas sodium hydride, and the amount of the base is usually 1 to 2 molerelative to 1 mole of a compound represented by the formula (2). Theamount of R¹OH used in the reaction is usually 1 to 1.2 moles relativeto 1 mole of a compound represented by the formula (2). The reactiontemperature is usually in a range of 0 to 80° C., and the reaction timeis usually in a range of 1 to 24 hours.

After completion of the reaction, the compound of the present inventioncan be obtained by subjecting the reaction mixture to post-treatmentprocedures such as organic solvent extraction, and concentration. Ifnecessary, the compound of the present invention can be further purifiedby subjecting to procedures such as chromatography.

The compound represented by the formula (2) can be prepared by reactinga compound represented by the formula (3) with an oxidizing agent.

wherein A, R², n and m are as defined above.

The reaction is usually performed in a solvent. Examples of the solventto be used include halogenated hydrocarbons such as chloroform anddichloromethane, and a mixture thereof. Examples of the oxidizing agentused in the reaction include peracids such as 3-chloroperoxybenzoicacid, and the amount of the oxidizing agent is usually 1 to 2.5 molesrelative to 1 mole of the compound represented by the formula (3). Thereaction temperature is usually in a range of −5° C. to roomtemperature, and the reaction time is usually in a range of 0.1 to 24hours.

After completion of the reaction, the compound represented by theformula (2) can be obtained by subjecting the reaction mixture topost-treatment procedures such as organic solvent extraction, andconcentration. If necessary, the compound can be further purified bysubjecting to procedures such as chromatography.

The compound represented by the formula (3) can be prepared by any ofthe following methods of (I) to (IV) depending on a kind of A in theformula (3).

(I) A process for preparing a compound represented by the formula (3) inwhich A is a single bond, by reacting5-chloro-3-methylthio-1,2,4-thiadiazole, and a phenylboronic acidcompound represented by the formula (4) or a trialkylphenyltin compoundrepresented by the formula (5) in the presence of a transition metalcompound.

wherein R² and n are as defined above, and R⁶ represents a C1-C4 alkylgroup.

The reaction is usually performed in a solvent under an atmosphere of aninert gas (nitrogen, argon etc.). Examples of the solvent used in thereaction include alcohols such as methanol, ethanol and 2-propanol,ethers such as 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, andmethyl-t-butyl ether, aromatic hydrocarbons such as benzene and toluene,ketones such as acetone, acid amides such as N,N-dimethylformamide,water, and a mixture thereof. Examples of the transition metal compoundused in the reaction include palladium (II) acetate,tetrakis(triphenylphosphine)palladium (0),{1,1′-bis(diphenylphosphino)ferrocene}dichloropalladium (II) anddichloro bis(triphenylphosphine)palladium(II), and the amount of thetransition metal compound is usually 0.001 to 0.1 mole relative to 1mole of 5-chloro-3-methylthio-1,2,4-thiadiazole. The amount of thephenylboronic acid compound represented by the formula (4) or thetrialkylphenyltin compound represented by the formula (5) used in thereaction is usually 0.9 to 1.5 mole relative to 1 mole of5-chloro-3-methylthio-1,2,4-thiadiazole. The reaction temperature of thereaction is usually in a range of room temperature to 150° C. Thereaction time is usually in a range of 1 to 12 hours.

The reaction can be performed by adding a base, if necessary. Examplesof the base which can be used include potassium phosphate, sodiumcarbonate, sodium bicarbonate, sodium acetate, potassium acetate andbarium hydroxide. In addition, the reaction can be performed by adding aphase transfer catalyst, if necessary. Examples of the phase transfercatalyst which can be used include a quaternary ammonium salt such astetrabutylammonium bromide, and benzyltrimethylammonium bromide.

After completion of the reaction, the objective product can be obtainedby subjecting the reaction mixture to post-treatment procedures such asorganic solvent extraction, and concentration. When thetrialkylphenyltin compound represented by the formula (5) is used in thereaction, the objecte product can be obtained by adding an aqueouspotassium fluoride solution to the reaction mixture, filtering theresulting precipitate, and concentrating the filtrate. The product canbe further purified by subjecting to procedures such as chromatography,if necessary.

(II) A process for preparing a compound represented by the formula (3)in which A is an oxygen atom, a sulfur atom or a NH group, by reacting5-chloro-3-methylthio-1,2,4-thiadiazole and a compound represented bythe formula (6) in the presence of a base.

wherein R² and n are as defined above and A¹ represents an oxygen atom,a sulfur atom or a NH group.

The reaction is usually performed in a solvent, and examples of thesolvent used in the reaction include ethers such as tetrahydrofuran,acid amides such as N,N-dimethylformamide, dimethyl sulfoxide, and amixture thereof. Examples of the base used in the reaction includeinorganic bases such as sodium hydride, and the amount of the base isusually 1 to 2 mole relative to 1 mole of5-chloro-3-methylthio-1,2,4-thiadiazole. The amount of the compoundrepresented by the formula (6) used in the reaction is usually 1 to 1.2mole relative to 1 mole of 5-chloro-3-methylthio-1,2,4-thiadiazole. Thereaction temperature is usually in a range of 0 to 80° C., and thereaction time is usually in a range of 1 to 24 hours.

After completion of the reaction, the objective product can be obtainedby subjecting the reaction mixture to post-treatment procedures such asorganic solvent extraction, and concentration. If necessary, the productcan be further purified by subjecting to procedures such aschromatography.

(III) A process for preparing a compound represented by the formula (3)in which A is a NR⁵ group, by reacting a compound represented by theformula (3) in which A is a NH group with R⁵X in the presence of a base.

wherein R², R⁵ and n are as defined above, and X represents a halogenatom.

The reaction is usually performed in a solvent. Examples of the solventused in the reaction include ethers such as tetrahydrofuran, acid amidessuch as N,N-dimethylformamide, dimethyl sulfoxide, and a mixturethereof. Examples of the base used in the reaction include inorganicbases such as sodium hydride, and the amount of the base is usually 1 to2 mole relative to 1 mole of a compound represented by the formula (3)in which A is a NR⁵ group. The amount of R⁵X used in the reaction isusually 1 to 1.2 mole relative to 1 mole of a compound represented bythe formula (3) in which A is a NR⁵ group. The reaction temperature isusually in a range of 0 to 80° C., and the reaction time is usually in arange of 1 to 12 hours.

After completion of the reaction, the objective product can be obtainedby subjecting the reaction mixture to post-treatment procedures such asorganic solvent extraction, and concentration. If necessary, the productcan be further purified by subjecting to procedures such aschromatography.

(IV) A process for preparing a compound represented by the formula (3),wherein A is a CR³R⁴ group, by reacting5-chloro-3-methylthio-1,2,4-thiadiazole and a compound represented bythe formula (7) in the presence of a transition metal compound.

wherein R²′ R³, R⁴ and n are as defined above.

The reaction is usually performed in a solvent, and examples of thesolvent used in the reaction include ethers such as tetrahydrofuran,acid amides such as N,N-dimethylformamide, dimethyl sulfoxide, and amixture thereof.

Examples of the transition metal compound used in the reaction includetetrakis(triphenylphosphine)palladium (0),{1,1′-bis(diphenylphosphino)ferrocene}dichloropalladium (II) anddichloro bis(triphenylphosphine)palladium (II), and the amount of thetransition metal compound is usually 0.001 to 0.1 mole relative to 1mole of 5-chloro-3-methylthio-1,2,4-thiadiazole.

The amount of a compound represented by the formula (7) used in thereaction is usually 1 to 1.2 mole relative to 1 mole of5-chloro-3-methylthio-1,2,4-thiadiazole.

The reaction temperature is usually in a range of 0 to 80° C., and thereaction time is usually in a range of 1 to 24 hours.

After completion of the reaction, the objective product can be obtainedby subjecting the reaction mixture to post-treatment procedures such asorganic solvent extraction, and concentration. If necessary, the productcan be further purified by subjecting to procedures such aschromatography.

Then, specific examples of the compound of the present invention areshown in Table 1. TABLE 1 Compound represented by the formula (1): (1)

Compound No. R¹ (R²)_(n) A 1 2-propynyl Unsubstituted Single bond 22-butynyl Unsubstituted Single bond 3 2-pentynyl Unsubstituted Singlebond 4 4,4-dimethyl- Unsubstituted Single bond 2-pentynyl 5 2-butynyl2-fluoro Single bond 6 2-butynyl 3-fluoro Single bond 7 2-butynyl4-fluoro Single bond 8 2-butynyl 2-chloro Single bond 9 2-butynyl3-chloro Single bond 10 2-butynyl 4-chloro Single bond 11 2-butynyl2,4-difluoro Single bond 12 2-butynyl 2,5-difluoro Single bond 132-butynyl 2,6-difluoro Single bond 14 2-butynyl 3,4-difluoro Single bond15 2-butynyl 3,5-difluoro Single bond 16 2-butynyl 2,3-difluoro Singlebond 17 2-butynyl 2-methyl Single bond 18 2-butynyl 3-methyl Single bond19 2-butynyl 4-methyl Single bond 20 2-butynyl 4-tert-butyl Single bond21 2-butynyl 3,5- Single bond bistrifluoromethyl 22 2-butynylUnsubstituted Oxygen atom 23 2-butynyl 2-fluoro Oxygen atom 24 2-butynyl3-fluoro Oxygen atom 25 2-butynyl 4-fluoro Oxygen atom 26 2-butynyl2-chloro Oxygen atom 27 2-butynyl 3-chloro Oxygen atom 28 2-butynyl4-chloro Oxygen atom 29 2-butynyl 2,4-difluoro Oxygen atom 30 2-butynyl2,5-difluoro Oxygen atom 31 2-butynyl 2,6-difluoro Oxygen atom 322-butynyl 3,4-difluoro Oxygen atom 33 2-butynyl 3,5-difluoro Oxygen atom34 2-butynyl 2,3-difluoro Oxygen atom 35 2-butynyl 2-methyl Oxygen atom36 2-butynyl 3-methyl Oxygen atom 37 2-butynyl 4-methyl Oxygen atom 382-butynyl 4-tert-butyl Oxygen atom 39 2-butynyl 3,5- Oxygen atombistrifluoromethyl 40 2-butynyl Unsubstituted CH₂ 41 2-butynyl 2-fluoroCH₂ 42 2-butynyl 3-fluoro CH₂ 43 2-butynyl 4-fluoro CH₂ 44 2-butynyl2-chloro CH₂ 45 2-butynyl 3-chloro CH₂ 46 2-butynyl 4-chloro CH₂ 472-butynyl 2,4-difluoro CH₂ 48 2-butynyl 2,5-difluoro CH₂ 49 2-butynyl2,6-difluoro CH₂ 50 2-butynyl 3,4-difluoro CH₂ 51 2-butynyl 2-chloro CH₂52 2-butynyl 3-chloro CH₂ 53 2-butynyl 4-chloro CH₂ 54 2-butynyl2,4-difluoro CH₂ 55 2-butynyl 2,5-difluoro CH₂ 56 2-butynyl 2,6-difluoroCH₂ 57 2-butynyl 3,4-difluoro CH₂ 58 2-butynyl 3,5-difluoro CH₂ 592-butynyl 2,3-difluoro CH₂ 60 2-butynyl 2-methyl CH₂ 61 2-butynyl3-methyl CH₂ 62 2-butynyl 4-methyl CH₂ 63 2-butynyl 4-tert-butyl CH₂ 642-butynyl 3,5- CH₂ bistrifluoromethyl 65 2-butynyl Unsubstituted NH 662-butynyl Unsubstituted NCH₃ 67 2-butynyl Unsubstituted NCH₂CH₃ 682-butynyl Unsubstituted NCH₂OCH₃ 69 2-butynyl Unsubstituted NCH₂OC₂H₅ 701-methyl-2- Unsubstituted Single bond butynyl 71 1-methyl-2-Unsubstituted Oxygen atom butynyl 72 1-methyl-2- 2-fluoro Single bondbutynyl 73 4-fluoro-2- Unsubstituted Single bond butynyl 74 2-pentynyl2-fluoro Single bond 75 2-pentynyl 3-fluoro Single bond 76 2-pentynyl4-fluoro Single bond 77 2-pentynyl 2-chloro Single bond 78 2-pentynyl3-chloro Single bond 79 2-pentynyl 4-chloro Single bond 80 2-pentynyl2,4-difluoro Single bond 81 2-pentynyl 2,5-difluoro Single bond 822-pentynyl 2,6-difluoro Single bond 83 2-pentynyl 3,4-difluoro Singlebond 84 2-pentynyl 3,5-difluoro Single bond 85 2-pentynyl 2,3-difluoroSingle bond 86 2-pentynyl 2-methyl Single bond 87 2-pentynyl 3-methylSingle bond 88 2-pentynyl 4-methyl Single bond 89 2-pentynyl4-tert-butyl Single bond 90 2-pentynyl 3,5- Single bondbistrifluoromethyl 91 2-butynyl 4-fluoro-3-methyl Single bond 922-butynyl 4-methyl-3-nitro Single bond 93 2-butynyl 4-methylthio Singlebond 94 2-butynyl 2-methoxy Single bond 95 2-butynyl 3-methoxy Singlebond 96 2-butynyl 4-methoxy Single bond 97 2-butynyl 2,3-dimethyl Singlebond 98 2-butynyl 3,5-dimethyl Single bond 99 2-butynyl 2,5-dimethylSingle bond 100 2-butynyl 3,5-dibromo Single bond 101 2-butynyl3-chloro-4-fluoro Single bond 102 2-butynyl 2,4-dichloro Single bond 1032-butynyl 2,3-dichloro Single bond 104 2-butynyl 2,5-dichloro Singlebond 105 2-butynyl 3,4-dichloro Single bond 106 2-butynyl 3,5-dichloroSingle bond 107 2-butynyl 2-bromo Single bond 108 2-butynyl 3-bromoSingle bond 109 2-butynyl 4-bromo Single bond 110 2-butynyl 3-nitroSingle bond 111 2-butynyl 4-trifluoromethyl Single bond 112 2-butynyl3-trifluoromethoxy Single bond 113 2-butynyl 4-trifluoromethoxy Singlebond 114 2-butynyl 3-cyano Single bond 115 2-butynyl 4-cyano Single bond116 2-pentynyl 4-fluoro3-methyl Single bond 117 2-pentynyl4-methyl-3-nitro Single bond 118 2-pentynyl 4-methylthio Single bond 1192-pentynyl 2-methoxy Single bond 120 2-pentynyl 3-methoxy Single bond121 2-pentynyl 4-methoxy Single bond 122 2-pentynyl 2,3-dimethyl Singlebond 123 2-pentynyl 3,5-dimethyl Single bond 124 2-pentynyl 2,5-dimethylSingle bond 125 2-pentynyl 3,5-dibromo Single bond 126 2-pentynyl3-chloro-4-fluoro Single bond 127 2-pentynyl 2,4-dichloro Single bond128 2-pentynyl 2,3-dichloro Single bond 129 2-pentynyl 2,5-dichloroSingle bond 130 2-pentynyl 3,4-dichloro Single bond 131 2-pentynyl3,5-dichloro Single bond 132 2-pentynyl 2-bromo Single bond 1332-pentynyl 3-bromo Single bond 134 2-pentynyl 4-bromo Single bond 1352-pentynyl 3-nitro Single bond 136 2-pentynyl 4-trifluoromethyl Singlebond 137 2-pentynyl 3-trifluoromethoxy Single bond 138 2-pentynyl4-trifluoromethoxy Single bond 139 2-pentynyl 3-cyano Single bond 1402-pentynyl 4-cyano Single bond

Examples of the harmful arthropod against which the compound of thepresent invention exhibits controlling effect are insects and mites,specifically, following ones.

Hemiptera insect pest: planthoppers such as small brown planthopper(Laodelphax striatellus), brown planthopper (Nilaparvata lugens) andwhite-backed rice planthopper (Sogatella furcifera), leafhoppers such asgreen rice leafhopper (Nephotettix cincticeps) and tea green leafhopper(Empoasca onukii), aphids such as cotton aphid (Aphis gossypii) andgreen peach aphid (Myzus persicae), stink bugs, whiteflies such asgreenhouse whitefly (Trialeurodes vaporariorum), sweet-potato whitefy(Bemisia tabaci) and silverleaf whitefly (Bemisia argentifolii), scales,lace bugs, jumping plantlice, etc.

Lepidoptera insect pest: pyralid moths such as rice stem borer (Chilosuppressalis), rice leafroller (Cnaphalocrocis medinalis), European cornborer (Ostrinia nubilalis) and bluegrass webworm (Parapediasiateterrella), owlet moths such as tabaco cutworm (Spodoptera litura),Spodoptera exigua, rice armyworm (Pseudaletia separata), cabbagearmyworm (Mamestra brassicae), black cutworm (Agrotis ipsilon),Trichoplusia spp., Heliothis spp., Helicoverpa spp. and Earias spp.,whites and sulfer butterflies such as common cabbage worm (Pieris rapaecrucivora), tortricid moths such as Adoxophyes orana fasciata,Grapholita molesta and codling moth (Cydia pomonella), Carposimidae suchas peach fruit moth (Carposina niponensis), Bucculatricidae such asLyonetia clerkella, leaf-blotch miners such as Phyllonorycterringoniella, Phyllochistinae such as Phyllocnistis citrella,Yponomeutidae such as diamondback moth (Plutela xylostella), gelechidmoths such as pink ball worm (Pectinophora gossypiella), Arctiidae,clothes moths, etc.

Diptera insect pest: mosquitos such as common mosquito (Culex pipienspallens), oriental latrine fly (Culex tritaeniorhynchus) and southernhouse mosquito (Culex quinquefasciatus), Aedes spp. such as Aedesaegypti and Aedes albopictus, Anophles spp. such as Anopheles sinensis,midges, house flies such as housefly (Musca domestica) and falsestablefly (Muscina stabulans), Calliphoridae, Sarcophagidae, littlehousefly, Anthomyiidae such as seedcrn maggot (Delia platura) and onionmaggot (Delia antiqua), fruit flies, small fruit flies, moth flies,black flies, Tabanidae, stable flies, leafminer flies, etc.

Coleoptera insect pest: corn rootworm such as western corn rootworm(Diabrotica virgifera virgifera) and southern corn rootworm (Diabroticaundecimpunctata howardi), scarabs such as cupreous chafer (Anomalacuprea) and soybean beetle (Anomala rufocuprea), weevils such as maizeweevil (Sitophilus zeamais), ricewater weevil (Lissorhoptrusoryzophilus) and adzuki bean weevil (Callosobruchuys chienensis),darkling beetles such as yellow mealworm (Tenebrio molitor) and redflour beetles (Tribolium castaneum), leaf beetles such as Oulema oryzae,cucurbit leaf beetle (Aulacophora femoralis), striped flea beetle(Phyllotreta striolata) and Colorado beetle (Leptinotarsa decemlineata),Anbiidae, Epilachna spp. such as twenty-eight-spotted ladbirds(Epilachna vigintioctopunctata), powderpost beetles, false powderpostbeetles, long-horned beetles, Paederus fuscipes, etc.

Thysanoptera insect pest: thrips such as Thrips spp. such as Thripspalmi, Frankliniella spp. such as western flower thrips (Frankliniellaoccidentalis), Sciltothrips ssp. such as yellow tea thrips (Sciltothripsdorsalis), Plaeothripidae, etc.

Hymenoptera insect pest: saufliws, ants, hornets, etc.

Dictyoptera insect pest: cockroachs, German cockroachs, etc.

Orthoptera insect pest: glasshoppers, mole crickets, etc.

Siphonaptera insect pest: feas, etc.

Anoplura insect pest: human body louse, etc.

Isoptera insect pest: termites, etc.

Acarina insect pest: spider mites etc.

The compound of the present invention has characteristic in controllingeffect against Hemiptera insect pests, Lepidopterta insect pests,Coleoptera insect pests and Thysanoptera insect pest.

The harmful arthropod controlling composition of the present inventionmay be the compound of the present invention itself. Usually, thecompound of the present invention and, for example, a solid carrier, aliquid carrier, a gaseous carrier and/or a bait (base material forpoison bait) are mixed, a surfactant and other adjuvants for formulationare added if necessary, and they are formulated into, for example, oils,emulsions, flowables, granules, powders, poison baits or microcapsulesto obtain the harmful arthropod controlling composition of the presentinvention. The formulation usually contains 0.01 to 95% by weight of thecompound of the present invention.

Examples of the solid carrier used for formulation into the compositioninclude fine powders or particles such as clays (kaolin clay,diatomaceous earth, synthetic hydrated silicon oxide, bentonite,fubasami clay, acid clay etc.), talc, ceramics, other inorganic minerals(sericite, quarts, sulfur, active carbon, calcium carbonate, hydratedsilica etc.), and chemical fertilizers (ammonium sulfate, ammoniumphosphate, ammonium nitrate, urea, ammonium chloride, etc.). Examples ofthe liquid carrier include water, alcohols (methanol, ethanol, etc.),ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons(benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.),aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.),esters (ethyl acetate, butyl acetate, etc.), nitrites (acetonitrile,isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acidamides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenatedhydrocarbons (dichloromethane, trichloroethane carbon tetrachloride,etc.), dimethyl sulfoxide, and vegetable oils (soybean oil, cottonseedoil, etc.), and examples of the gaseous carrier include fluorocarbon,butane gas, LPG (liquefied petroleum gas), dimethyl ether and carbondioxide gas. Examples of a surfactant include alkyl sulfate salts, alkylsulfonic acid salts, alkylaryl sulfonic acid salts, alkylaryl ethers andtheir polyoxyethylene derivatives, polyethylene glycols ethers,polyhydric alcohol esters and sugar alcohol derivatives. Examples ofadjuvants for formulation include sticker, dispersants and stabilizers,specifically, casein, gelatin, polysaccharides (starch powder, gumarabic, cellulose derivative, alginic acid etc.), lignin derivative,bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol,polyvinylpyrrolidone, polyacrylic acid, etc.), PAP (acidic isopropylphosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),vegetable oil, mineral oil, fatty acid and fatty acid ester. Examples ofthe base of a poison bait include a bait ingredient such as cerealpowder, vegetable oil, sugar and crystalline cellulose, and antioxidantsuch as dibutylhydroxytoluene and nordihydroguaialetic acid,preservative such as dehydroacetic acid, agent for preventing erroneouseating by children or pets such as red pepper powder, and insect pestattracting perfume such as cheese perfume, onion perfume, and peanutsoil.

The harmful arthropod controlling composition of the present inventionis used by applying to harmful arthropods or a place where harmfularthropods inhibit. For example, when a harmful arthropod parasitizing acultivating plant is controlled, the arthropod can be controlled byscattering the harmful arthropod controlling composition of the presentinvention on a ground part of the cultivating plant, or by pouring theharmful arthropod controlling composition of the present invention overa root part of the cultivating plant.

When the harmful arthropod controlling composition of the presentinvention is used, the application amount is usually 0.1 to 1,000 g per1,000 m² in terms of the compound of the present invention. Emulsions,wettable powders, flowables and microcapsules are usually applied bydiluting with water so that the active ingredient concentration becomes10 to 10,000 ppm, and granules and powders are usually applied as theyare.

Alternatively, the harmful arthropod controlling composition of thepresent invention can be used together with other insecticide,nematicide, acaricide, fungicide, herbicide, plant growth regulatingagent, synergist, fertilizer, soil conditioner, animal feed, etc.

Examples of such insecticide, acaricide and nematicide includeorganophosphorous compounds such as fenitrothion, fenthion,pyridafenthion, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate,methidathion, disulfoton, DDVP, sulprofos, profenofos, cyanophos,dioxabenzofos, dimethoate, phenthoate, malathion, trichlorfon, azinphos-methyl, monocrotophos, dicrotophos, ethion, fosthiazate; carbamatecompounds such as BPMC, benfuracarb, propoxur, carbo sulfan, carbaryl,methomyl, ethiofencarb, aldicarb, oxamyl, fenothiocarb, and thiodicarb;pyrethroid compounds such as etofenprox, fenvalerate, esfenvalerate,fenpropathrin, cypermethrin, α-cypermethrin, Z-cypermethrin, permethrin,cyhalothrin, λ-cyhalothrin, cyfluthrin, β-cyfluthrin, deltamethrin,cycloprothrin, τ-fluvalinate, flucythrinate, bifenthrin, acrinathrin,tralomethrin, silafluofen and halfenprox; neonicotinoid compound suchacetamiprid, thiamethoxam and thiacloprid; benzoylphenylurea compoundssuch as chlorfluazuron, teflubenzuron, fulfenoxuron and lufenuron;benzoylhydrazide compounds such as tebufenozide, holofenozide,methoxyfenozide and chromafenozide; thiadiazine compounds such asbuprofezin; nereistoxin compounds such as cartap, thiocyclam, bensultap;chlorinated hydrocarbon compounds such as endosulfan, γ-BHC, and1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; formamidine compounds suchas amitraz, and chlordimeform; thiourea compounds such as diafenthiuron;phenylpyrazole compounds; chlorfenapyr, pymetrozine, spinosad,indoxacarb, bromopropylate, tetradifon, chinomethionat, propargite,fenbutatin oxide, hexythiazox, etoxazole, clofentezine, pyridaben,fenpyroximate, tebufenpyrad, pyrimidifen, fenazaquin, acequinocyl,bifenazate, fluacrypyrim, spirodichlofen, milbemectin, avermectin,emamectin benzoate, azadirachtin[AZAD], polynactine complex[tetranactin, dinactin, trinactin].

The present invention will be explained more detail below by way ofPreparation Examples, Formulation Examples and Test Examples, but thepresent invention is not limited to these examples. In addition, ¹H-NMRdata in Preparation Examples, and Reference Preparation Examples weremeasured in deuteride chloroform solvent using tetramethylsilane as aninternal standard. In Preparation Examples, No. of the compound of thepresent invention indicates that shown in aforementioned Table 1.

PREPARATION EXAMPLE 1

To 3 ml of N,N-dimethylformamide were added 160 mg of a mixture of3-methylsulfinyl-5-phenyl-1,2,4-thiadiazole and3-methylsulfonyl-5-phenyl-1,2,4-thiadiazole (integration ratio of ¹H-NMRsulfonyl form:sulfinyl form=4:1) and 60 mg of propargyl alcohol, and tothe resulting mixture was added 43 mg of sodium hydride (60% oily) withice-cooling. The mixture was stirred for 20 minutes with ice-cooling,and allowed to stand at room temperature for 18 hours. Then, thereaction mixture was poured into an aqueous saturated sodium chloridesolution, and the mixture was extracted with t-butyl methyl ether. Theorganic layer was concentrated, and the resulting residue was subjectedto silica gel column chromatography to obtain 100 mg of5-phenyl-3-propargyloxy-1,2,4-thiadiazole (the compound (1) of thepresent invention).

mp: 66.9° C.

¹H-NMR: 2.55 (t, 1H), 5.10 (d, 2H), 7.48-7.54 (m, 3H), 7.91-7.94 (m, 2H)

PREPARATION EXAMPLE 2

To 3 ml of N,N-dimethylformamide were added 300 mg of a mixture of3-methylsulfinyl-5-phenyl-1,2,4-thiadiazole and3-methylsulfonyl-5-phenyl-1,2,4-thiadiazole (integration ratio of ¹H-NMRsulfonyl form:sulfinyl form=4:1) and 141 mg of 2-butyne-1-ol, and to theresulting mixture was added 80 mg of sodium hydride (60% oily) withice-cooling. The mixture was stirred for 10 minutes with ice-cooling,and allowed to stand at room temperature for 18 hours. Then, thereaction mixture was poured into an aqueous saturated sodium chloridesolution, and the mixture was extracted with t-butyl methyl ether. Theorganic layer was concentrated, and the resulting residue was subjectedto silica gel column chromatography to obtain 200 mg of5-phenyl-3-(2-butynyloxy)-1,2,4-thiadiazole (the compound (2) of thepresent invention).

mp: 70.3° C.

¹H-NMR: 1.88 (t, 3H), 5.05 (q, 2H), 7.45-7.53 (m, 3H), 7.91-7.93 (m, 2H)

PREPARATION EXAMPLE 3

3-Methylthio-5-(2,3-difluorophenyl)-1,2,4-thiadiazole was dissolved in14 ml of chloroform, and 279 mg of m-chloroperoxybenzoic acid (65%<) wasadded thereto. The mixture was stirred for 7 hours with ice-cooling, andallowed to stand at room temperature overnight. Then, the reactionmixture was added to an aqueous sodium bicarbonate solution, and layerswere separated. The organic layer was concentrated. Further, toluene wasadded to the residue, and the mixture was concentrated. To the resultingresidue were added 2 ml of N,N-dimethylformamide and 59 mg of2-butyne-1-ol, and 59 mg of sodium hydride (60% oily) was added theretowith ice-cooling. The mixture was stirred at the same temperature for 30minutes, and further stirred at room temperature for 3 hours. Then, thereaction mixture was poured into an aqueous saturated sodium chloridesolution, and the mixture was extracted with t-butyl methyl ether. Theresidue obtained by concentration of the organic layer was purified bysilica gel column chromatography to obtain 95 mg of5-(2,3-difluorophenyl)-3-(2-butynyloxy)-1,2,4-thiadiazole (the compound(16) of the present invention).

¹H-NMR: 1.88 (t, 3H), 5.07 (q, 2H), 7.24-7.36 (m, 2H), 8.04-8.09 (m, 1H)

PREPARATION EXAMPLE 4

To 2 ml of N,N-dimethylformamide were added 295 mg of a mixture of3-methylsulfinyl-5-(2-fluorophenyl)-1,2,4-thiadiazole and3-methylsulfonyl-5-(2-fluorophenyl)-1,2,4-thiadiazole (integration ratioof ¹H-NMR sulfonyl form:sulfinyl form=4:1) and 85 mg of 2-butyne-1-ol,to the resulting mixture was added 55 mg of sodium hydride (60% oily)with ice-cooling, and the mixture was stirred for 10 minutes, andfurther stirred at room temperature for 3 hours. The reaction mixturewas poured into an aqueous saturated sodium chloride solution, and themixture was extracted with t-butyl methyl ether. The organic layer wasconcentrated, and the residue was subjected to silica gel columnchromatography to obtain 227 mg of5-(2-fluorophenyl)-3-(2-butynyloxy)-1,2,4-thiadiazole (the compound (5)of the present invention).

¹H-NMR: 1.88 (t, 3H), 5.07 (q, 2H), 7.20-7.33 (m, 2H), 7.48-7.56 (m,1H), 8.29-8.35 (m, 1H)

PREPARATION EXAMPLE 5

In 3 ml of N,N-dimethylformamide, 350 mg of3-methylsulfonyl-5-(3-fluorophenyl)-1,2,4-thiadiazole and 105 mg of2-butyne-1-ol were dissolved, to the resulting solution was added 65 mgof sodium hydride (60% oily) with ice-cooling, and the mixture wasstirred for 10 minutes, and further stirred at room temperature for 4hours. Then, the reaction mixture was poured into an aqueous saturatedsodium chloride solution, and the mixture was extracted with t-butylmethyl ether. The residue obtained by concentration of the organic layerwas subjected to silica gel column chromatography to obtain 289 mg of5-(3-fluorophenyl)-3-(2-butynyloxy)-1,2,4-thiadiazole (the compound (6)of the present invention).

mp: 68.7° C.

¹H-NMR: 1.88 (t, 3H), 5.06 (q, 2H), 7.12-7.25 (m, 1H), 7.42-7.50 (m,1H), 7.64-7.70 (m, 1H)

PREPARATION EXAMPLE 6

In 2.5 ml of N,N-dimethylformamide, 350 mg of3-methylsulfonyl-5-(3-chlorophenyl)-1,2,4-thiadiazole and 98 mg of2-butyne-1-ol were dissolved, to the resulting solution was added 56 mgof sodium hydride (60% oily) with ice-cooling, and the mixture wasstirred for 30 minutes, and further stirred at room temperature for 1hour. Then, the reaction mixture was poured into an aqueous saturatedsodium chloride solution, and the mixture was extracted with t-butylmethyl ether. The residue obtained by concentration of the organic layerwas subjected to silica gel column chromatography to obtain 290 mg of5-(3-chlorophenyl)-3-(2-butynyloxy)-1,2,4-thiadiazole (the compound (9)of the present invention).

¹H-NMR: 7.94 (s, 1H), 7.78 (d, 1H), 7.48 (d, 1H), 7.42 (t, 1H), 5.05 (q,2H), 1.88 (t, 3H)

PREPARATION EXAMPLE 7

In 2.5 ml of N,N-dimethylformamide, 350 mg of3-methylsulfonyl-5-(3-chlorophenyl)-1,2,4-thiadiazole and 117 mg of2-pentyne-1-ol were dissolved, to the resulting solution was added 56 mgof sodium hydride (60% oily) with ice-cooling, and the mixture wasstirred for 30 minutes, and further stirred at room temperature for 1hour. Then, the reaction mixture was poured into an aqueous saturatedsodium chloride solution, and the mixture was extracted with t-butylmethyl ether. The residue obtained by concentration of the organic layerwas subjected to silica gel column chromatography to obtain 290 mg of5-(3-chlorophenyl)-3-(2-pentynyloxy)-1,2,4-thiadiazole (the compound(78) of the present invention).

¹H-NMR: 7.94 (s, 1H), 7.78 (d, 1H), 7.48 (d, 1H), 7.42 (t, 1H), 5.05 (q,2H), 1.88 (t, 3H)

PREPARATION EXAMPLE 8

In 3 ml of N,N-dimethylformamide, 400 mg of a mixture of3-methylsulfonyl-5-(2-chlorophenyl)-1,2,4-thiadiazole and3-methylsulfinyl-5-(2-chlorophenyl)-1,2,4-thiadiazole and 114 mg of2-butyne-1-ol were dissolved, to the resulting solution was added 65 mgof sodium hydride (60% oily) with ice-cooling, and the mixture wasstirred for 1 hour, and further stirred at room temperature for 1 hour.Then, the reaction mixture was poured into an aqueous saturated sodiumchloride solution, and the mixture was extracted with t-butyl methylether. The residue obtained by concentration of the organic layer wassubjected to silica gel column chromatography to obtain 210 mg of5-(2-chlorophenyl)-3-(2-butynyloxy)-1,2,4-thiadiazole (the compound (8)of the present invention).

¹H-NMR: 8.51 (d, 1H), 7.53 (d, 1H), 7.46 (m, 2H), 5.06 (q, 2H), 1.88 (t,3H)

PREPARATION EXAMPLE 9

In 3 ml of N,N-dimethylformamide, 400 mg of a mixture of3-methylsulfonyl-5-(2-chlorophenyl)-1,2,4-thiadiazole and3-methylsulfinyl-5-(2-chlorophenyl)-1,2,4-thiadiazole, and 136 mg of2-pentyne-1-ol were dissolved, to the resulting solution was added 65 mgof sodium hydride (60% oily) with ice-cooling, and the mixture wasstirred for 1 hour, and further stirred at room temperature for 1 hour.Then, the reaction mixture was added to an aqueous saturated sodiumchloride solution, and the mixture was extracted with t-butyl methylether. The residue obtained by concentration of the organic layer wassubjected to silica gel column chromatography to obtain 220 mg of5-(2-chlorophenyl)-3-(2-pentynyloxy)-1,2,4-thiadiazole (the compound(77) of the present invention).

¹H-NMR: 8.52 (d, 1H), 7.53 (d, 1H), 7.45 (m, 2H), 5.08 (q, 2H), 2.25 (m,2H), 1.15 (t, 3H)

Then, a process for preparing an intermediate compound of the compoundof the present invention will be described as Reference PreparationExample.

REFERENCE PREPARATION EXAMPLE 1

In 30 ml of chloroform, 455 mg of3-methylthio-5-phenyl-1,2,4-thiadiazole was dissolved, to the resultingsolution was added 377 mg of 3-chloroperoxybenzoic acid (65%<), and themixture was stirred for 7 hours with ice-cooling. Then, the reactionmixture was added to an aqueous sodium bicarbonate solution, and thelayers were separated. The organic layer was dried over anhydrous sodiumsulfate, and concentrated to obtain 520 mg of a mixture of3-methylsulfinyl-5-phenyl-1,2,4-thiadiazole and3-methylsulfonyl-5-phenyl-1,2,4-thiadiazole. This product was used inthe next step without further purification.

¹H-NMR: 3.13 (sulfinylmethyl s, 3H), 3.44 (sulfonylmethyl s, 3H), 7.55(m, 3H), 8.00 (m, 2H)

Sulfonyl form:sulfinyl form=1:4

REFERENCE PREPARATION EXAMPLE 2

In 10 ml of chloroform, 330 mg of3-methylthio-5-(2-fluorophenyl)-1,2,4-thiadiazole was dissolved, to theresulting solution was added 722 mg of 3-chloroperoxybenzoic acid (65%<)with ice-cooling, and the mixture was allowed to stand at roomtemperature for 18 hours. Then, the reaction mixture was poured into anaqueous sodium bicarbonate solution, and the layers were separated. Theorganic layer was dried over anhydrous sodium sulfate, and concentratedto obtain 295 mg of a mixture of3-methylsulfinyl-5-(2-fluorophenyl)-1,2,4-thiadiazole and3-methylsulfonyl-5-(2-fluorophenyl)-1,2,4-thiadiazole. This product wasused in the next step without further purification.

¹H-NMR: 3.13 (sulfinylmethyl s, 3H), 3.45 (sulfonylmethyl s, 3H),7.29-7.41 (m, 2H), 7.59-7.65 (m, 1H), 8.41-8.46 (m, 1H) sulfonylform:sulfinyl form=4:1

REFERENCE PREPARATION EXAMPLE 3

In 8 ml of chloroform, 360 mg of3-methylthio-5-(3-fluorophenyl)-1,2,4-thiadiazole was dissolved, to theresulting solution was added 982 mg of 3-chloroperoxybenzoic acid (65%<)with ice-cooling, and the mixture was stirred at room temperature for 7hours. The reaction mixture was poured into an aqueous sodium sulfitesolution, and the layers were separated. The organic layer was washedwith an aqueous sodium bicarbonate solution, dried over anhydrous sodiumsulfate, and concentrated to obtain 520 mg of3-methylsulfonyl-5-(3-fluorophenyl)-1,2,4-thiadiazole.

¹H-NMR: 3.45 (s, 3H), 7.27-7.47 (m, 1H), 7.49-7.58 (m, 1H), 7.73-7.81(m, 1H)

REFERENCE PREPARATION EXAMPLE 4

To 30 ml of toluene were added 500 mg of5-chloro-3-methylthio-1,2,4-thiadiazole, 794 mg of trimethylphenyltinand 346 mg of tetrakistriphenylphosphine palladium, and the mixture washeated under reflux for 8 hours in a nitrogen atmosphere. Then, thereaction mixture was cooled to room temperature, and a 20% aqueouspotassium fluoride solution was added to the reaction mixture, followedby stirring. This mixture was filtered through Celite, and the filtratewas concentrated. The resulting residue was subjected to silica gelcolumn chromatography to obtain 455 mg of3-methylthio-5-phenyl-1,2,4-thiadiazole.

mp: 57.1° C.

REFERENCE PREPARATION EXAMPLE 5

To 4 ml of 1,2-dimethoxyethane were added 300 mg of5-chloro-3-methylthio-1,2,4-thiadiazole, 427 mg of2,3-difluorophenylboronic acid, 104 mg of tetrakistriphenylphosphinepalladium and 4 ml of a 2 M aqueous sodium carbonate solution, and themixture was stirred at 60° C. for 9 hours in a nitrogen atmosphere.Then, the reaction mixture was poured into an aqueous saturated sodiumchloride solution, and the mixture was extracted with t-butyl methylether. The residue obtained by concentration of the organic layer wassubjected to silica gel column chromatography to obtain 170 mg of3-methylthio-5-(2,3-difluorophenyl)-1,2,4-tihadiazole.

¹H-NMR: 2.73 (s, 3H), 7.26-7.38 (m, 2H), 8.05-8.11 (m, 1H)

REFERENCE PREPARATION EXAMPLE 6

To 4 ml of 1,2-dimethoxyethane were added 284 mg of5-chloro-3-methylthio-1,2,4-thiadiazole, 262 mg of 2-fluorophenylboronicacid, 98 mg of tetrakistriphenylphosphine palladium and 4 ml of a 2 Maqueous sodium carbonate solution, and the mixture was stirred at 80° C.for 12 hours in a nitrogen atmosphere. Then, the reaction mixture waspoured into an aqueous saturated sodium chloride solution, and themixture was extracted with t-butyl methyl ether. The residue obtained byconcentration of the organic layer was subjected to silica gel columnchromatography to obtain 330 mg of3-methylthio-5-(2-fluorophenyl)-1,2,4-thiadiazole.

¹H-NMR: 2.74 (s, 3H), 7.21-7.34 (m, 2H), 7.49-7.56 (m, 1H), 8.30-8.36(m, 1H)

REFERENCE PREPARATION EXAMPLE 7

To 5 ml of 1,2-dimethoxyethane were added 400 mg of5-chloro-3-methylthio-1,2,4-thiadiazole, 335 mg of 3-fluorophenylboronicacid, 139 mg of tetrakistriphenylphosphine palladium and 4 ml of a 2 Maqueous sodium carbonate solution, and the mixture was heated underreflux for 2 hours in a nitrogen atmosphere. Then, the reaction mixturewas poured into water, and the mixture was extracted with t-butyl methylether. The residue obtained by concentration of the organic layer wassubjected to silica gel column chromatography to obtain 360 mg of3-methyothio-5-(3-fluorophenyl)-1,2,4-thiadiazole.

REFERENCE PREPARATION EXAMPLE 8

To 25 ml of 1,2-dimethoxyethane were added 2.0 g of5-chloro-3-methylthio-1,2,4-thiadiazole, 2.25 g of 3-chlorophenylboronicacid, 694 mg of tetrakistriphenylphosphine palladium and about 25 ml ofa 2 M aqueous sodium carbonate solution, and the mixture was heatedunder reflux for 3 hours in a nitrogen atmosphere. Then, the reactionmixture was poured into water, and the mixture was extracted witht-butyl methyl ether. The organic layer was dried with anhydrous sodiumsulfate, and the residue obtained by concentration was subjected tosilica gel column chromatography to obtain 1.48 g of3-methylthio-5-(2-chlorophenyl)-1,2,4-thiadiazole.

¹H-NMR: 7.95 (s, 1H), 7.78 (d, 1H), 7.49 (d, 1H), 7.42 (t, 1H), 2.73 (s,3H)

REFERENCE PREPARATION EXAMPLE 9

In 12 ml of chloroform, 1.5 g of3-methylthio-5-(3-chlorophenyl)-1,2,4-thiadiazole was dissolved, to theresulting solution was slowly added 5.85 g of 3-chloroperoxybenzoic acid(65%<) with ice-cooling, and the mixture was stirred for 30 minutes withice-cooling, and at room temperature for 2 hours. The reaction mixturewas poured into an aqueous sodium sulfite solution, and the layers wereseparated. The organic layer was washed with an aqueous sodiumbicarbonate solution, dried over anhydrous sodium sulfate, andconcentrated to obtain 1.44 g of3-methylsulfonyl-5-(3-chlorophenyl)-1,2,4-thiadiazole.

¹H-NMR: 8.04 (s, 1H), 7.88 (d, 1H), 7.59 (d, 1H), 7.7.49 (t, 1H), 3.32(s, 3H)

REFERENCE PREPARATION EXAMPLE 10

To 25 ml of 1,2-dimethoxyethane were added about 2.0 g of5-chloro-3-methylthio-1,2,4-thiadiazole, 2.25 g of 2-chlorophenylboronicacid, 694 mg of tetrakistriphenylphosphine palladium and 25 ml of a 2 Maqueous sodium carbonate solution, and the mixture was heated underreflux for 3 hours in a nitrogen atmosphere. Then, the reaction mixturewas poured into water, and the mixture was extracted with t-butyl methylether. The organic layer was dried over anhydrous sodium sulfate, andthe residue obtained by concentration was subjected to silica gel columnchromatography to obtain 1.67 g of3-methylthio-5-(3-chlorophenyl)-1,2,4-thiadiazole.

REFERENCE PREPARATION EXAMPLE 11

In 30 ml of chloroform, 1.5 g of3-methylthio-5-(2-chlorophenyl)-1,2,4-thiadiazole was dissolved, to theresulting solution was slowly added 3.05 g of 3-chloroperoxybenzoic acid(70%<) with ice-cooling, and the mixture was stirred for 30 minutes withice-cooling, and at room temperature for 2 hours. The reaction mixturewas poured into an aqueous sodium sulfite solution, and the layers wereseparated. The organic layer was washed with an aqueous sodiumbicarbonate solution, dried over anhydrous sodium sulfate, andconcentrated to obtain 1.61 g of a mixture of3-methylsulfonyl-5-(2-chlorophenyl)-1,2,4-thiadiazole and3-methylsulfinyl-5-(2-chlorophenyl)-1,2,4-thiadiazole.

¹H-NMR: 8.64-8.58 (m), 7.60-7.48 (m), 3.45 (s), 3.13 (s)

sulfonyl form:sulfinyl form=about 2.7:1

Then, Formulation Examples will be shown. Hereinafter, parts representparts by weight and the compound of the present invention is expressedby compound No. shown in Table 1.

FORMULATION EXAMPLE 1 Emulsion

In 37.5 parts of xylene and 37.5 parts of dimethylformamide, 9 parts ofeach of the compounds (1) to (140) of the present invention isdissolved, 10 parts of polyoxyethylenestyryl phenyl ether and 6 parts ofcalcium dodecylbenzenesulfonate are added thereto, and the mixture isthoroughly stirred and mixed to obtain an emulsion.

FORMULATION EXAMPLE 2 Wettable Powder

To a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calciumlignin sulfonate, 20 parts of a synthetic hydrated silicon oxide finepowder and 65 parts of diatomaceous earth, 9 parts of each of thecompounds (1) to (140) of the present invention is added, and themixture is thoroughly stirred and mixed to obtain a wettable powder.

FORMULATION EXAMPLE 3 Granule

A mixture of 3 parts of each of the compounds (1) to (140) of thepresent invention, 5 parts of a synthetic hydrated silicon oxide finepowder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentoniteand 57 parts of clay is thoroughly stirred and mixed, and an appropriateamount of water is added to the mixture. The mixture is further stirred,subjected to granulation with a granulator, and air-dried to obtain agranule.

FORMULATION EXAMPLE 4 Powder

A mixture of 4.5 parts of each of the compounds (1) to (140) of thepresent invention, 1 part of a synthetic hydrated silicon oxide finepowder, 1 part of Dolires B (Sankyo Co., Ltd.) as a coagulating agent,and 7 parts of clay is thoroughly mixed with a mortar, and then stirredand mixed with a juice mixer. To the resulting mixture is added 86.5parts of cut clay, and the mixture is thoroughly stirred and mixed toobtain a powder.

FORMULATION EXAMPLE 5

A mixture of 10 parts of each of the compounds (1) to (140), 35 parts ofwhite carbon containing 50 parts of polyoxyethylene alkyl ether sulfateammonium salt, and 55 parts of water is finely ground by a wet grindingmethod to obtain a preparation.

Then, Test Examples demonstrate that the compound of the presentinvention is effective as an active ingredient of a harmful arthropodcontrolling composition.

TEST EXAMPLE 1

A preparation prepared from each of the compounds (1), (2), (5), (6) and(16) of the present invention according to Formulation Example 5 wasdiluted with water so that the concentration of the compound of thepresent invention became 500 ppm to obtain a test scattering solution.

On the other hand, soil was filled in a polyethylene cups, cucumber wasplanted in each cup, and grown until its first foliage leaves developed.About 20 cotton aphids (Aphis gossypii) were made parasitic on thecucumber. After one day, the aforementioned test scattering solution wasscattered on the cucumber at a ratio of 20 ml/cup. Six days afterscattering, the number of cotton aphids was examined, and a controllingvalue was calculated by the following equation.Controlling value (%)={1−(Cb×Tai)/(Cai×Tb)}×100wherein Cb represents the number of insects of an untreated group beforetreatment, Cai represents the number of insects of an untreated group atthe time of observation, Tb represents the number of insects of atreated group before treatment, and Tai represents the number of insectsof a treated group at the time of observation, respectively.

As a result, all of the compounds (1), (2), (5), (6) and (16) of thepresent invention showed a controlling value of 90% or more,respectively.

TEST EXAMPLE 2

A preparation prepared from each of the compound (1) of the presentinvention and a comparative compound (A) according to FormulationExample 5 was diluted with water so that the concentration of thecompound of the present invention became 500 ppm to obtain a testscattering solution.

On the other hand, soil was filled into polyethylene cups, cucumber wasplanted in each cup, and grown until its first foliage leaves developed.The aforementioned test scattering solution was scattered on thecucumber at a ratio of 20 ml/cup, and the scattered solution on thesurface of the leaf was dried. The first foliage leaf was cut off,placed on a filter (diameter 70 mm) impregnated with water in apolyethylene cup (diameter 110 mm), 30 larvae of western flower thrips(Frankliniella occidentalis) were released thereon, and the polyethylenecup was closed with a lid. After seven days, a damage degree of thecucumber leaf by western flower thrips (Frankliniella occidentalis) wasexamined.

As a result, a damage area rate by western flower thrips (Frankliniellaoccidentalis) in the leaf treated with the compound (1) of the presentinvention was within 5%. A damage area rate in the leaf treated with thecomparative compound (A) was 20% or more.

TEST EXAMPLE 3

A preparation prepared from each of the compounds (1), (2), (5), (6),(8), (9), (16), (77) and (78) of the present invention and thecomparative compound (A) according to Formulation Example 5 was dilutedwith water so that the concentration of the compound of the presentinvention became 500 ppm to obtain a test scattering solution.

On the other hand, soil was filled in polyethylene cups, cabbage wasplanted in each cup, and grown until its first foliage leaves developed,and leaves other than a first foliage leaves were removed. About 200imagoes of silverleaf whitefly (Bemisia argentifolii) were released onthis cabbage for about 24 hours, and had them lay eggs on the cabbagefirst foliage leaf.

The thus obtained cabbage on which about 80 to 100 eggs of silverleafwhitefly (Bemisia argentifolii) were laid was allowed to stand in agreenhouse for 8 days, and the aforementioned test scattering solutionwas scattered at a ratio of 20 ml/cup. Seven days after scattering, thenumber of alive insects was examined, and an insecticidal rate wascalculated. As a result, the compounds (1), (2), (5), (6), (8), (9),(16), (77) and (78) of the present invention showed an insecticidal rateof 90% or more. The comparative compound (A) showed an insecticidal rateof 30% or less.

The comparative compound (A) used in Test Example 2 and Test Example 3is a compound represented by the following formula described inDE3030661 (compound 9 in the table on page 47).

INDUSTRIAL APPLICABILITY

By using the compound of the present invention, harmful arthropods canbe controlled.

1. A 1,2,4-thiadiazole compound represented by the formula (1):

wherein R¹ represents a C3-C7 alkynyl group optionally substituted withone or more halogen atom(s), R represents a halogen atom, a C1-C4 alkylgroup, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxygroup, a C1-C4 alkylthio group, a cyano group or a nitro group, nrepresents an integer of 0 to 5, provided that, when n represents aninteger of 2 or more, respective R²s may be the same or different, Arepresents an oxygen atom, a sulfur atom, a single bond, a CR³R⁴ groupor a NR⁵ group, R³ and R⁴ represent each independently a hydrogen atomor a C1-C4 alkyl group, and R⁵ represents a hydrogen atom, a C1-C7 alkylgroup, a haloalkyl group, a C2-C4(alkoxyalkyl) group, aC2-C4(haloalkoxyalkyl) group, a C3-C6 alkenyl group, a C3-C6 haloalkenylgroup, a C3-C7 alkynyl group, a C3-C7 haloalkynyl group or a cyanomethylgroup.
 2. The 1,2,4-thiadiazole compound according to claim 1, wherein Ain the formula (1) is a single bond.
 3. The 1,2,4-thiadiazole compoundaccording to claim 1, wherein R¹ in the formula (1) is a 2-propynylgroup, a 2-butynyl group or 2-pentynyl group.
 4. The 1,2,4-thiadiazolecompound according to claim 1, wherein R¹ in the formula (1) is a2-butynyl group or a 2-pentynyl group.
 5. A composition for controllinga harmful arthropod which comprises an effective amount of the1,2,4-thiadiazole compound according to claim
 1. 6. A method forcontrolling a harmful arthropod which comprises applying, to harmfularthropods or a place where harmful arthropods inhabit, a1,2,4-thiadiazole compound represented by the formula (1):

wherein R¹ represents a C3-C7 alkynyl group optionally substituted withone or more halogen atom(s), R represents a halogen atom, a C1-C4 alkylgroup, a C1-C4 haloalkyl group, a C1-C4 alkoxy group, a C1-C4 haloalkoxygroup, a C1-C4 alkylthio group, a cyano group or a nitro group, nrepresents an integer of 0 to 5, provided that, when n represents aninteger of 2 or more, respective R²s may be the same or different, Arepresents an oxygen atom, a sulfur atom, a single bond, a CR³R⁴ groupor a NR⁵ group, R³ and R⁴ represent each independently a hydrogen atomor C1-C4 alkyl group, and R⁵ represents a hydrogen atom, a C1-C7 alkylgroup, a haloalkyl group, a C2-C4(alkoxyalkyl) group, aC2-C4(haloalkoxyalkyl) group, a C3-C6 alkenyl group, a C3-C6 haloalkenylgroup, a C3-C7 alkynyl group, a C3-C7 haloalkynyl group or a cyanomethylgroup.
 7. The controlling method according to claim 6, wherein theharmful arthropod is a Hemiptera insect pest, a Lepidoptera insect pest,a Coleoptera insect pest or a Thysanoptera insect pest.
 8. Thecontrolling method according to claim 6, wherein the harmful arthropodis a Hemiptera insect pest or a Thysanoptera insect pest.
 9. Use of the1,2,4-thiadiazole compound according to claim 1 as an active ingredientof a composition for controlling a harmful arthropod.
 10. The1,2,4-thiadiazole compound according to claim 2, wherein R¹ in theformula (1) is a 2-propynyl group, a 2-butynyl group or 2-pentynylgroup.
 11. The 1,2,4-thiadiazole compound according to claim 2, whereinR¹ in the formula (1) is a 2-butynyl group or a 2-pentynyl group.